Anthraquinone vat dyestuff



Patented Nov. 6, 1923. v

v 1,690,236 PATENT-OFFICE.

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I Drawing. Application filed January 20, 1088, Serlirl No. 82,588, and in January 21,1985.

vat dyestufi' on heating 220 C. with alummum chloride which is converted into a This invention relates to the preparation of vat dyestuffs of the anthraqulnoneseries by submitting certain anthra u inone derivatives to an aluminum chloride fusion in the presence of a cyclic compound containing a tertiary nitrogen atom, i. e., a nitrogen atom having three valence bonds attached to carbon, and to certain new products prepared according to this process.

In several German patents, as for example, 136,015, 240,080, 249,000 and 262,788,

the fusion of anthraquinone derivatives with aluminum chloride is described. In

' these patents, the substances are heated to temperatures of 220 to 270 C. in admixture. with a large excess of aluminum chloride, (upfto partsb weight). V s

We have foun that such fusions can be carried. out not only with smaller amounts of aluminum chloride, as for example, with only one part by weight, but also that it 2 taining'a tertiary nitrogen atom such as py-.

' mixedwith one to four times its weight of dry can be carried out at 'considerably lower temperatures if aluminum chloride isu'sedin the presence of cyclic compounds con-*- ridine, quinoline, dimethylanilin, etc. For example, anhydrous aluminum chloride is pyridine, and a'very well crystallizing com- 9 pound of both components, which is solu ble in excess pyridine, is obtained'with evolution of heat,'=and then the substance that is to be fused is introduced with stirring. Then it is uickly heated to the reaction temperature w ich .18 about 100 C: lower than in the case of; the acid aluminum chloride melts. The'reactio'n roduct is thus obtained partly in the orm'of a le'uco-compound from which it can be easilyisolated y treatment with the oxygen ofair; I The process just described presents very important advanta'ges over the processes of the patents mentioned. Besides" the d1mi-..

nution of the amount ofaluminum chloride, the' frothjng .w ich is verygreat in the case of the acid me -s and which makes the process difiicult, islessenedQarid mostimportant of all, the presentprocess yields very cureproducts directly. in excellent yields due to lower reaction temperature and the presence: of a base whereby the injurious "effects of free hydrochloric acid at high temperatures are avoided, While 'forex; unplgaceo to Patent 240,080, 1. 1 v dianthraqmnon'ylaunne jellies-brawn aluminum chloride fusion with the'same results. For. example, according to German Patent.206,464 a reddish-brown vat dyestulf is obtained by the action of aluminum 01110? J ride on 2-aminoanthraquinone with nitrobenzolas a diluent, whereas when pyridine 1s used in' place of nitrobenzene, flavanthrene results at about 180 0. (Example 6). v Flavanthrene when prepared by melt-' in 2-aminoanthraquinone 'with aluminum chloridealone, is obtained only at temperatures of 250,. to 280 0. (German Patent 136,015); The mvention is illustrated by the followlng examples Emamj)le 1.

Ten parts by weight of anhydrous aluminum' chloride are mixed with 40 parts by weight of dry pyridine by stirring. Solution results with development of alarge amount of heat, andthe temperature must eventually be maintained below the boiling point of pyridine by cooling. Then ten parts by weight of 1.1" 'dianthfraquinon lamine are' introduced and the mixture is eated for a short time with stirring to a'temperature oi about 120 C. until everything is dissolved. The olive-colored melt while still warm. is stirred into 1000 parts by weight of about 3% caustic sodaand in this way a' part of the reaction product sinto solution forming an orange vat. an oxidation is brought about by vigorous stirring in'the' air at about 70 C. Finally, it is boi d and the recipitated yellow dyestufi is isolated by in verygood yields. It" s'esses the characteristics of the dyestu of Example '1 of German Patent 251,021, is soluble with extreme' diflicul in high vents, yields 00 'redicolore solutions in moon-- concentrated sul e acid and d es cotton froze -vats in fast .WYQHOY s ades. It-

organic solprobably possesses a carbazole structure corresponding probably to the formula:

drosultite solution vat as in Example 2, and reprecipitated by oxidation.

E atample 5?.

Ten parts by weight of 4-be'nzoylamine 1.1 dianthraquinonylamine are suspended in 50 parts by weight of pyridine, 16 parts by weight of anhydrous aluminum chloride are introduced and the mixture is heated for about twenty minutes to 125 C. until a homogenous olive-brown melt results. The mixture is worked up by stirring it into dilute caustic soda which contains the amount of hydrosulfite necessary to reduce the dyestutt' formed, and then the reaction product is separated by blowing in air and filtering the vat. The dyestutf is obtained in good yields and is somewhat more easily soluble. in organic solvents than the products of Example 1. It yields brown colored solutions in concentrated sulfuric acid. It dyes cotton very fast brown shades from cold and warm vats, and corresponds probably to the formula:

0 II I C Q C O O=O 6 crystallizes from aniline in line orange needles which yield a cherry-red solution in concentrated sulfuric acid. Cotton is dyed fast orange-yellow shades from brown-rcd vats. By treating the dyestufi' paste with sodium hypochlorite solution even greater clearness of shade can he arrived at.

Five parts by weight of the dianthra quinonylamine derivative obtained by condensing 4-brom-L9 anthraquinone-methy1- pyridone with l-aminoanthraquinone are heated in admixture with 12 parts by weight of pyridine and 10 parts by weight of anhydrous aluminum chloride for about 45 minutes at MSG-180 C. with stirring. The reaction product is isolated as described above. It dissolves in boiling nitrobenzol only with difficulty and crystallizes from this solution in fine orange needles which yield deep red solutions in concentrated sulfuric acid. It produces fast brownish-orange dyeings on cotton from both cold and warm vats and corresponds probably to the formula:

0 Example 5. Ten parts by weight of 1.1 dianthraare introduced at aboiit 100 G. into a solution x of 20 parts by weight of anhydrous aluminum chloride in 40 parts by weight of pyridine and the temperature is imaintained for a short time with stirring at 125130 C. The melt soon becomes very viscous and can be worked up after coolin as in Example 2 by treat ment in an alka ine hydrosulfite vat solution, in which the reaction product dissolves easily yielding a yellow-brown solution. The resultin dyestufi' which probably possesses the iormu a:

dissolves only with greatidifliculty in concentrated sulfuric .acld producing a'h'right olive colorand is precipitated from.- t is solution in the form of reddish-brown flakes by means of water. These-flakes yield very fast and deep reddish-brown dyeings on cotton; It differs essentially from the product of German Patent 208,969, which is obtained by melting the same raw materials with potash,

which yields brown solutions in'sulfuric acid and a yellow brown prtcipitate' from siich a solution by addition of water, and which dyes cotton tobacco brown shades which are co siderably paler.

dyestuif-which is identical with. the product of this exahnplav Ewample 6.

Five parts by weight of 2-aminoanthraquinone are stirred into the warm mixture of '10 parts by weight of aluminum chloride and 10 parts by weight of pyridine, and the melt isheated for about 30 minutes to 170190 C.

By piirifying from sulfuric acid-for example, it can be converted into a' until it has become viscous. On introducing the .meltinto a warm alkaline hydrosulfite 'solution, the resulting flavanthrene which probably possesses the formula o can then be precipitated in orange flakes by blowing in air,'if necessary, after filtering ofl'impurities.

The products produced according to my invention are very superior to products pro duced by the rocesses of aluminum chloride into solution with a deep blue color and fusion hereto ore used.. The products of Ex-.

.amples 1 and 5 are purer and are obtained in better yields than by the fusion process using aluminum chloride only. All of the dyestuffs described in Examples 1 to 5 belong to the carbazole class and are outstandingly fast; I claim:

1. Process of producing vat dyestufls of the anthraquinone series which consists in reacting with anhydrous aluminum chloride upon an anthraquinone derivative corresponding to the general formula:

in which R=stands for an anthraquinonyl residue and R for hydrogen [or an anthra quinonyl residue, in the presence of substantial amounts of a cyclic compound containing a tertiary nitrogen atom different from the anthraquinone derivative reacted upon.

the anthraquinone series which consists in 2. Processof producing vat dyestuffs of" reacting with anhydrous aluminum chloride upon an anthraquinone derivative corresponding to the general formula:

in which R stands for aiiantlir'aquinonyl residue and Rim hydrogen or an anthra @quinonyl residue,'in the presence of substantial amountsjof a compound. containing a.

pyridine nucleua 3. Process of producing vat dyestufl's of the anthraquinone series which consists in reacting with anhydrous aluminum chloride upon an anthraqulnone derivative correspending to the general formula:

of substantial amounts of a compound containing a pyridine nucleus.

6. Process of producing vat dyestuffs of the anthraquinone series which consists in reacting with anhydrous aluminum chloride upon a dianthraquinonylamine in presence of substantial amounts of pyridine. 7. Process of producing vat dyestuffs of the anthraquinone series which consists in reacting with anhydrous aluminum chloride upon a 1-2'-dianthraquinonylamine in presence of substantial amounts of pyridine.

8. As a new product the vat dyestuff which is obtainable by treating 12-dianthraquinonylainine with anhydrous aluminum chloride in presence of pyridine, which is chemically most likely a carbazol derivative, which is an orange colored crystalline compound, soluble in concentrated sulfuric acid with a cherry color and dyeing cotton orangeyellow fast shades from brown-red vats.

In testimony whereof I have hereunto set my hand.

WALTER MIEG. 

